EP1701792A1 - Novel heteropolyacid catalyst and method for producing the same - Google Patents
Novel heteropolyacid catalyst and method for producing the sameInfo
- Publication number
- EP1701792A1 EP1701792A1 EP05704433A EP05704433A EP1701792A1 EP 1701792 A1 EP1701792 A1 EP 1701792A1 EP 05704433 A EP05704433 A EP 05704433A EP 05704433 A EP05704433 A EP 05704433A EP 1701792 A1 EP1701792 A1 EP 1701792A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- heteropolyacid
- transition metal
- heteropolyacid catalyst
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000299 transition metal carbonate Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 transition metal salt Chemical class 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 3
- 239000011646 cupric carbonate Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102100021888 Helix-loop-helix protein 1 Human genes 0.000 description 1
- 101000897691 Homo sapiens Helix-loop-helix protein 1 Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02F—DREDGING; SOIL-SHIFTING
- E02F5/00—Dredgers or soil-shifting machines for special purposes
- E02F5/30—Auxiliary apparatus, e.g. for thawing, cracking, blowing-up, or other preparatory treatment of the soil
- E02F5/305—Arrangements for breaking-up hard ground
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
Definitions
- the present invention relates to a phosphomolybdate-based heteropolyacid catalyst which is useful in vapor-phase oxidation of methacrolein, as represented by the following formula 1 : PMO a A b B c C d D e E f Og (1) wherein A, B, C, D, E, a, b, c, d, e, f, and g are as defined in below.
- the present invention also relates to a method for producing the heteropolyacid catalyst.
- a heteropolyacid catalyst with a composition of M0 12 P01- 3 M01- 3 C110 ⁇ -2 V 0 ⁇ -2 Xoo ⁇ -2 Y a Ob M is K, Rb, or Cs; X is Ba, La, Ga, Al, Ag, Cd, Ti, Tl, Hg, Pb, or Zn; Y is Fe, Co, Ni, Sr, Mn, In, Ta, Ge, S, or Be) is useful for the oxidation of methacrolein.
- the heteropolyacid catalyst with the above-described composition is produced to a final catalyst by drying, forming into a predetermined shape, and calcination.
- pellets with a diameter of 5 mm and a length of 5 mm are generally formed.
- Decomposable ammonium or nitrate species are decomposed by the heat treatment to complete a catalyst with a desired structure and composition.
- the calcination is performed at a temperature of 300-500 ° C under an oxygen or nitrogen atmosphere.
- U.S. Patent No. 4,621,155 describes that the preparation of a heteropolyacid catalyst in the presence of an N-containing material such as pyridine, piperidine, and piperazine can enhance formabihty and physical strength of the catalyst and reproducibility of the catalyst preparation.
- a heteropolyacid catalyst production method varies according to the type of a metal-containing catalyst precursor. However, ammonium paramolybdate and ammonium metavanadate are mainly used. According to a catalyst production method disclosed in Example 1 of U.S.
- Patent No. 6,333,293B1 ammonium paramolybdate and ammonium metavanadate are dissolved in heated water with stirring and an appropriate amount of 85% phosphoric acid is added thereto. Then, cesium nitrate and copper nitrate are added to the resultant solution followed by heating and drying to produce a catalyst.
- U.S. Patent No. 6,458,740B2 discloses a method for producing a heteropolyacid catalyst including adding pyridine and 85% phosphoric acid to a solution containing ammonium paramolybdate and ammonium metavanadate, adding nitric acid, cesium nitrate, and copper nitrate to the resultant solution to induce coprecipitation, followed by heating and drying.
- the present inventors found a method for producing a heteropolyacid catalyst by preparing an ammonium ion- containing heteropolyacid using nitric acid followed by addition of a metal precursor, unlike a conventional catalyst production method by coaddition and coprecipitation of a transition metal and nitric acid.
- a transition metal carbonate instead of a common transition metal nitrate, is used as the metal precursor, dispersion of a m etal component i s e nhanced, t hereby i ncreasing catalyst a ctivity.
- the p resent inventors thus completed the present invention.
- the present invention provides a novel heteropolyacid catalyst represented by formula 1.
- the present invention also provides a method for efficiently producing the heteropolyacid catalyst of the formula 1.
- a heteropolyacid catalyst represented by the following formula 1 : PMOaAbBc D e EfOg (1) wherein A is N, ⁇ b, or W; B is an alkaline metal or an alkaline earth metal; C is Cu, Ag, Co, ⁇ i, Pb, Mn, or Tl; D is Fe, Ce, Cr, Sn, Zn, Pd, or Rh; E is an organic acid or a N-containing compound; a is 5-12; b is 0.01-5; c is 0.01-3; d is 0.01-3; e is 0-0.3; f is 0-10; and g is a number satisfying the valence requirements of a, b, c, d, e, and f.
- the heteropolyacid catalyst of the formula 1 may have a composition of PM ⁇ 2 V 0.3 ⁇ Cs ⁇ 2 Cu 0.1 .- ) .5 Feo.o ⁇ .-o . ⁇ O x where x is a number satisfying the valence requirements.
- a transition metal nitrate may be further added.
- the transition metal carbonate and/or nitrate may be added at a temperature of 20-60 ° C .
- Particles formed on a surface of the heteropolyacid catalyst may have a particle size of 20-100 nm.
- Methacrylic acid which is a product of the oxidation of methacrolein by a heteropolyacid catalyst according to the present invention is used as a monomer of polymethylmethacrylate.
- the composition of the h eteropolyacid catalyst of the formula 1 is based on phosphomolybdate represented by the formula, H 3 PM ⁇ 2 O 0 .
- Phosphomolybdate has a Keggin structure in which one phosphate is surrounded by 12 octahedral molybdenum (Mo) oxides sharing edges.
- the molybdenum (Mo) may be partially or wholly substituted by oxide of the A element. That is, catalyst activity can be modified by an electron effect while maintaining the same catalyst structure as phosphomolybdate.
- the number of cations to be bonded is determined by the oxidation state or amount of an element to be substituted. For example, when a Mo +6 ion is substituted by a N +5 ion, the number of cations to be bonded is increased from 3 to 4.
- the hydrogen ions can be substituted by alkaline metals, alkaline earth metals, transition metals, ammonium ions, or pyridine ions.
- the elements B, C, and D of the formula 1 represent substituted cations.
- the substituted cations create a secondary or tertiary structure of a catalyst. Therefore, catalyst physical properties such as surface area, pore volume, and pore distribution can be adjusted, thereby increasing catalyst performance.
- a catalyst is dried at a temperature of 100- 150 ° C .
- a dried catalyst is extruded on an extruder to prepare a catalyst with a predetermined shape. Extrusion is a very important process determining the physical strength of a catalyst.
- An extruded catalyst has a cylindrical shape with a diameter of about 5 mm and a length of about 5 mm.
- the cylindrical catalyst is calcined in a furnace at 350-500 ° C in an air or nitrogen atmosphere for a predetermined time. During the calcination, nitrogen oxide contained in a catalyst precursor, such as ammonia and nitrate, is removed. Also, pyridine is partially removed and combined water is gradually removed.
- the most representative B element is a transition metal Cs
- the most representative C element is a metal Cu
- the most representative D element is a metal Fe.
- Cs and Cu are derived from carbonate precursors which are commercially available. Fe is derived from a nitrate precursor and the nitrate precursor is used in a small amount in catalyst production.
- the present inventors found that a catalyst with hexahedral crystal faces obtained by reaction of a previously prepared ammonium ion-containing heteropolyacid with a carbonate precursor is the most efficient catalyst. In this respect, when an ammonium ion-containing heteropolyacid is prepared and then reaction of the ammonium ion-containing heteropolyacid with a carbonate precursor is performed, a high efficiency catalyst can be produced.
- a method for producing a heteropolyacid catalyst according to an embodiment of the present invention will now be described schematically.
- Step (a) (NH ) 6 Mo 7 O 2 , (NH 4 )VO , and H 3 PO, and pyridine in some cases are mixed to prepare an aqueous solution. That is, ammonium paramolybdate ((NH ) 6 Mo O 24 ) and ammonium metavanadate ((NH 4 )VO 4 ) are dissolved in distilled water and H 3 PO 4 is added thereto with stirring. Pyridine is selectively added to the resultant solution and stirred to prepare an aqueous solution.
- Step (b) Nitric acid is added to the resultant solution of step (a) to prepare an ammonium ion-containing heteropolyacid. That is, HNO 3 is gradually dropwise added to the resultant solution of step (a) to make slurry. The slurry is stirred to prepare the ammonium ion-containing heteropolyacid.
- Step (c) Transition metal carbonate and/or nitrate is/are added to the ammonium ion- containing heteropolyacid o btained i n s tep (b).
- step (b) That i s, Cu(OH) 2 • CuCO 3 , Cs 2 CO 3 , and optionally Fe(NO 3 ) 3 are added to the ammonium ion-containing heteropolyacid obtained in step (b) at 20-60 ° C and heated to 70 ° C to increase catalyst dispersibility and activity.
- Step (d) A catalyst-containing solution obtained in step (c) is dried and calcined in an air atmosphere. That is, the catalyst-containing solution obtained in step (c) is subjected to removal of excess water in a rotary evaporator and dried in an oven. Then, the resultant product is mixed with a glass fiber and formed into a pellet of 5 mm (diameter) x 5 mm (length), followed by calcination, to produce a catalyst with a particle size of 150-250 m.
- the transition metal carbonate and/or nitrate is/are added at a temperature of 20-60 ° C .
- FIG. 1 is a surface Scanning Electron Microscopy (SEM) image of a catalyst prepared in Example 2 according to the present invention.
- FIG. 2 is a surface SEM image of a catalyst prepared in Example 3 according to the present invention.
- FIG. 3 is a surface SEM image of a catalyst prepared in Comparative Example 1.
- FIG. 4 is a surface SEM image of a catalyst prepared in Comparative Example 2.
- FIG. 5 is a surface SEM image of a common catalyst of Comparative Example 3.
- Example 1 100 g of ammonium paramolybdate ((NH ) 6 Mo O 24 ) and 3.0 g of ammonium metavanadate ((NH 4 )VO 4 ) were dissolved in 440 ml of 80 ° C distilled water. 23 g of pyridine and 6.4 g of 85% H 3 PO 4 were added thereto with stirring. A solution of 60 ml of HNO 3 in 100 ml of H 2 O was gradually dropwise added to the resultant solution to make slurry.
- Example 2 A catalyst was prepared in the same manner as in Example 1 except that 1.04 g of Fe(NO 3 ) 3 was further added, in addition to 1.7 g (7.7 mmol) of Cu(OH) 2 • CuCO 3 and 12.55g (38.5 mmol) Cs 2 CO 3 .
- the prepared catalyst had the composition of
- Example 3 A catalyst was prepared in the same manner as in Example 2 except that pyridine was not used. A surface SEM image of the catalyst is shown in FIG. 2.
- Example 1 A catalyst was prepared in the same manner as in Example 1 except that 3.6g (15.4 mmol) of Cu(NO 3 ) 2 and 15.0g (77 mmol) of CsNO 3 were used instead of 1.7g (7.7 mmol) of Cu(OH) 2 • CuCO 3 and 12.55g (38.5 mmol) of Cs 2 CO 3 .
- a surface SEM image of the catalyst is shown in FIG. 3.
- Comparative Example 2 A catalyst was prepared in the same manner as in Comparative Example 1 except that the transition metal precursors and nitric acid underwent coprecipitation like U.S. Patent No. 6,458,740B2. A surface SEM image of the catalyst is shown in FIG. 4.
- Catalytic reaction results for the catalysts of Examples 1-3 and Comparative Examples 1-3 are presented in Table 1 below.
- Catalytic reaction was performed under the composition of 3.6 mol% of methacrolein (MACR), 10 mol% of H 2 O, 9.2 mol% of O 2 , and balance N 2 .
- a dose of a used catalyst was lg.
- the reaction temperature was 280-320 °C .
- a product was quantified by Gas Chromatography (GC).
- the catalysts prepared in Examples 1-3 according to the present invention exhibited remarkably excellent conversion rate, selectivity, and yield, as compared with the catalysts of Comparative Examples 1-3 according to conventional technologies.
- particles of 20 to 100 nm in size were uniformly distributed on surfaces of the catalysts, relative to the catalysts of Comparative Examples 1-3. This shows that transition metal ions were uniformly dispersed.
- a heteropolyacid catalyst of the present invention is excellent in conversion rate, selectivity, and yield, relative to that produced by a conventional heteropolyacid catalyst production technology. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
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Abstract
Provided is a novel heteropolyacid catalyst useful for partial oxidation of methacrolein (MACR) to methacrylic acid (MAA), as represented by the following formula 1: PMoaAbBcCdDeEfOg (1) wherein A, B, C, D, E, a, b, c, d, e, f, and g are as defined in the specification. Provided is also a method for producing the heteropolyacid catalyst. The heteropolyacid catalyst produced by the method exhibits excellent catalyst activity in terms of conversion rate, selectivity, and yield.
Description
NOVEL HETEROPOLYACID CATALYST AND METHOD FOR PRODUCING THE SAME
Technical Field The present invention relates to a phosphomolybdate-based heteropolyacid catalyst which is useful in vapor-phase oxidation of methacrolein, as represented by the following formula 1 : PMOaAbBcCdDeEfOg (1) wherein A, B, C, D, E, a, b, c, d, e, f, and g are as defined in below. The present invention also relates to a method for producing the heteropolyacid catalyst.
Background Art Japanese companies such as Nippon Shokubai C hemical Ltd. (NSCL) hold a majority of patents about a heteropolyacid catalyst for partial oxidation of methacrolein to m ethacrylic a cid b y a v apor-phase o xidation p rocess. In t hese p atents, a c atalyst precursor is mainly prepared by coprecipitation with nitric acid or by vacuum drying in the absence of nitric acid. Meanwhile, U.S. Patent No. 4,301,031 describes that a heteropolyacid catalyst with a composition of M012P01-3M01-3C110 ι-2V0 ι-2Xooι-2YaOb (M is K, Rb, or Cs; X is Ba, La, Ga, Al, Ag, Cd, Ti, Tl, Hg, Pb, or Zn; Y is Fe, Co, Ni, Sr, Mn, In, Ta, Ge, S, or Be) is useful for the oxidation of methacrolein. The heteropolyacid catalyst with the above-described composition is produced to a final catalyst by drying, forming into a predetermined shape, and calcination. During the forming into a predetermined shape, pellets with a diameter of 5 mm and a length of 5 mm are generally formed. Decomposable ammonium or nitrate species are decomposed by the heat treatment to
complete a catalyst with a desired structure and composition. The calcination is performed at a temperature of 300-500 °C under an oxygen or nitrogen atmosphere. U.S. Patent No. 4,621,155 describes that the preparation of a heteropolyacid catalyst in the presence of an N-containing material such as pyridine, piperidine, and piperazine can enhance formabihty and physical strength of the catalyst and reproducibility of the catalyst preparation. A heteropolyacid catalyst production method varies according to the type of a metal-containing catalyst precursor. However, ammonium paramolybdate and ammonium metavanadate are mainly used. According to a catalyst production method disclosed in Example 1 of U.S.
Patent No. 6,333,293B1, ammonium paramolybdate and ammonium metavanadate are dissolved in heated water with stirring and an appropriate amount of 85% phosphoric acid is added thereto. Then, cesium nitrate and copper nitrate are added to the resultant solution followed by heating and drying to produce a catalyst. A catalyst production method disclosed in Example 12 of U.S. Patent No.
4,558,028 follows the same manner as in Example 1 of U.S. Patent No. 6,333,293B1 except that an appropriate amount of 85% phosphoric acid is added together with an appropriate amount of pyridine, and nitric acid is added before the addition of cesium nitrate and copper nitrate. U.S. Patent No. 6,458,740B2 discloses a method for producing a heteropolyacid catalyst including adding pyridine and 85% phosphoric acid to a solution containing ammonium paramolybdate and ammonium metavanadate, adding nitric acid, cesium nitrate, and copper nitrate to the resultant solution to induce coprecipitation, followed by heating and drying. This patent describes that activity and selectivity of a catalyst are affected by the ratio of NH4/Mθι2 and NH4/NO contained in catalyst precursors.
Meanwhile, Korean Patent No. 1996-0003796 describes that transition metal ions such as Cu ion can be efficiently precipitated using a mixture of pyridine with oxalic acid. In spite of these many inventions, since common heteropolyacid catalysts have low activity, there is an increased need to improve the conversion rate of methacrolein or selectivity to methacrylic acid. Furthermore, there is a problem in that productivity is lowered due to the low yield of a catalyst. In addition, formation of a Keggin structure is prerequisite for production of a heteropolyacid catalyst. Reaction of a molybdenum precursor, a vanadium precursor, and a phosphoric acid partially forms a precipitate but these components are partially present in their dissolved forms in water. At this time, when the pH of the solution is lowered using nitric acid or the like, crystals are created and precipitated. When nitric acid is dropwise added in the absence of a transition metal, an ammonium ion- containing heteropolyacid is formed. At this time, nitric acid can be precipitated together with another transition metal, which is called coprecipitation. Therefore, a Keggin anion structure is created and bonds with another transition metal as a cation to form a precipitate. Generally, it is known that coprecipitation leads to uniform precipitation of a transition metal. However, in a heteropolyacid production process, precipitation by nitric acid and transition metal salt formation are simultaneously performed, and thus, there is a high likelihood of non-uniform precipitation. Some transition metals may not form water-insoluble salts of them with heteropolyacid at low pH. Copper is the most representative metal. In this respect, as described above, even though coprecipitation is used for preparation of a heteropolyacid catalyst, copper ions remain in their dissolved forms without being
precipitated and makes a blue color solution. To solve these problems, a prepared catalyst slurry is dried in vacuum or heated above the boiling point of water so that metal ions are uniformly distributed in a catalyst simultaneously with drying of the slurry.
Disclosure of Invention While searching for solutions to these problems, the present inventors found a method for producing a heteropolyacid catalyst by preparing an ammonium ion- containing heteropolyacid using nitric acid followed by addition of a metal precursor, unlike a conventional catalyst production method by coaddition and coprecipitation of a transition metal and nitric acid. At this time, when a transition metal carbonate, instead of a common transition metal nitrate, is used as the metal precursor, dispersion of a m etal component i s e nhanced, t hereby i ncreasing catalyst a ctivity. The p resent inventors thus completed the present invention. Therefore, the present invention provides a novel heteropolyacid catalyst represented by formula 1. The present invention also provides a method for efficiently producing the heteropolyacid catalyst of the formula 1. The above and other objects of the present invention can be accomplished by embodiments of the present invention as will be described hereinafter. According to an aspect of the present invention, there is provided a heteropolyacid catalyst represented by the following formula 1 : PMOaAbBc DeEfOg (1) wherein A is N, Νb, or W; B is an alkaline metal or an alkaline earth metal; C is Cu, Ag, Co, Νi, Pb, Mn, or Tl; D is Fe, Ce, Cr, Sn, Zn, Pd, or Rh; E is an organic acid
or a N-containing compound; a is 5-12; b is 0.01-5; c is 0.01-3; d is 0.01-3; e is 0-0.3; f is 0-10; and g is a number satisfying the valence requirements of a, b, c, d, e, and f. The heteropolyacid catalyst of the formula 1 may have a composition of PMθι2V0.3~ Csι~2Cu0.1.- ).5Feo.oι.-o.ιOx where x is a number satisfying the valence requirements. According to another aspect of the present invention, there is provided a method for producing the heteropolyacid catalyst represented by the formula 1, the method including: (a) mixing (NH4)6Mo7O24, (NH4)VO4, and H PO, and pyridine in some cases, to prepare an aqueous solution; (b) adding nitric acid to the solution of step (a) to prepare an ammonium ion- containing heteropolyacid; (c) adding a transition metal carbonate to a solution obtained in step (b); and (d) drying and calcining a catalyst-containing solution obtained in step (c) in an air atmosphere. In step (c), a transition metal nitrate may be further added. In step (c), the transition metal carbonate and/or nitrate may be added at a temperature of 20-60 °C . Particles formed on a surface of the heteropolyacid catalyst may have a particle size of 20-100 nm. Hereinafter, the present invention will be described in detail. Methacrylic acid which is a product of the oxidation of methacrolein by a heteropolyacid catalyst according to the present invention is used as a monomer of polymethylmethacrylate. The composition of the h eteropolyacid catalyst of the formula 1 is based on
phosphomolybdate represented by the formula, H3PMθι2O 0. Phosphomolybdate has a Keggin structure in which one phosphate is surrounded by 12 octahedral molybdenum (Mo) oxides sharing edges. The molybdenum (Mo) may be partially or wholly substituted by oxide of the A element. That is, catalyst activity can be modified by an electron effect while maintaining the same catalyst structure as phosphomolybdate. The number of cations to be bonded is determined by the oxidation state or amount of an element to be substituted. For example, when a Mo+6 ion is substituted by a N+5 ion, the number of cations to be bonded is increased from 3 to 4. The hydrogen ions can be substituted by alkaline metals, alkaline earth metals, transition metals, ammonium ions, or pyridine ions. The elements B, C, and D of the formula 1 represent substituted cations. The substituted cations create a secondary or tertiary structure of a catalyst. Therefore, catalyst physical properties such as surface area, pore volume, and pore distribution can be adjusted, thereby increasing catalyst performance. Generally, a catalyst is dried at a temperature of 100- 150 °C . A dried catalyst is extruded on an extruder to prepare a catalyst with a predetermined shape. Extrusion is a very important process determining the physical strength of a catalyst. In this respect, an appropriate amount of water, a glass fiber for reinforcement of catalyst strength, etc. may be used for extrusion. An extruded catalyst has a cylindrical shape with a diameter of about 5 mm and a length of about 5 mm. The cylindrical catalyst is calcined in a furnace at 350-500 °C in an air or nitrogen atmosphere for a predetermined time. During the calcination, nitrogen oxide contained in a catalyst precursor, such as ammonia and nitrate, is removed. Also, pyridine is partially removed and combined water is gradually removed. In the heteropolyacid catalyst of the formula 1, the most representative B
element is a transition metal Cs, the most representative C element is a metal Cu, and the most representative D element is a metal Fe. Cs and Cu are derived from carbonate precursors which are commercially available. Fe is derived from a nitrate precursor and the nitrate precursor is used in a small amount in catalyst production. The present inventors found that a catalyst with hexahedral crystal faces obtained by reaction of a previously prepared ammonium ion-containing heteropolyacid with a carbonate precursor is the most efficient catalyst. In this respect, when an ammonium ion-containing heteropolyacid is prepared and then reaction of the ammonium ion-containing heteropolyacid with a carbonate precursor is performed, a high efficiency catalyst can be produced. A method for producing a heteropolyacid catalyst according to an embodiment of the present invention will now be described schematically.
Step (a) (NH )6Mo7O2 , (NH4)VO , and H3PO, and pyridine in some cases are mixed to prepare an aqueous solution. That is, ammonium paramolybdate ((NH )6Mo O24) and ammonium metavanadate ((NH4)VO4) are dissolved in distilled water and H3PO4 is added thereto with stirring. Pyridine is selectively added to the resultant solution and stirred to prepare an aqueous solution.
Step (b) Nitric acid is added to the resultant solution of step (a) to prepare an ammonium ion-containing heteropolyacid. That is, HNO3 is gradually dropwise added to the resultant solution of step (a) to make slurry. The slurry is stirred to prepare the ammonium ion-containing heteropolyacid.
Step (c) Transition metal carbonate and/or nitrate is/are added to the ammonium ion- containing heteropolyacid o btained i n s tep (b). That i s, Cu(OH)2 • CuCO3, Cs2CO3, and optionally Fe(NO3)3 are added to the ammonium ion-containing heteropolyacid obtained in step (b) at 20-60 °C and heated to 70 °C to increase catalyst dispersibility and activity.
Step (d) A catalyst-containing solution obtained in step (c) is dried and calcined in an air atmosphere. That is, the catalyst-containing solution obtained in step (c) is subjected to removal of excess water in a rotary evaporator and dried in an oven. Then, the resultant product is mixed with a glass fiber and formed into a pellet of 5 mm (diameter) x 5 mm (length), followed by calcination, to produce a catalyst with a particle size of 150-250 m. Preferably, the transition metal carbonate and/or nitrate is/are added at a temperature of 20-60 °C . If the addition temperature of the transition metal carbonate and/or nitrate is less than 20 °C , separate cooling is required and a production cost increases. On the other hand, if it exceeds 60 °C , decomposition of carbonate may occur. Hereinafter, the present invention will be described more specifically by Examples. However, the following Examples are provided only for illustrations and thus the present invention is not limited to or by them.
Brief Description of the Drawings FIG. 1 is a surface Scanning Electron Microscopy (SEM) image of a catalyst prepared in Example 2 according to the present invention. FIG. 2 is a surface SEM image of a catalyst prepared in Example 3 according to the present invention. FIG. 3 is a surface SEM image of a catalyst prepared in Comparative Example 1. FIG. 4 is a surface SEM image of a catalyst prepared in Comparative Example 2. FIG. 5 is a surface SEM image of a common catalyst of Comparative Example 3.
Modes for Carrying Out the Invention [Example 1] 100 g of ammonium paramolybdate ((NH )6Mo O24) and 3.0 g of ammonium metavanadate ((NH4)VO4) were dissolved in 440 ml of 80 °C distilled water. 23 g of pyridine and 6.4 g of 85% H3PO4 were added thereto with stirring. A solution of 60 ml of HNO3 in 100 ml of H2O was gradually dropwise added to the resultant solution to make slurry. 1.7 g of Cu(OH)2 ■ Q1CO3 arid 12.55 g of Cs2CO3 were added to the slurry at 40 °C with stirring and incubated at 70 °C . Then, the resultant solution was subjected to removal of excess water in a rotary evaporator and dried in a 120°C oven. The dried product was mixed with 5 g of a glass fiber, formed into pellets of 5 mm (diameter) x 5 mm (length), calcined at 400 °C for 5 hours, and pulverized, to produce a catalyst with a particle size of 150-250 μ .
[Example 2] A catalyst was prepared in the same manner as in Example 1 except that 1.04 g of Fe(NO3)3 was further added, in addition to 1.7 g (7.7 mmol) of Cu(OH)2 • CuCO3
and 12.55g (38.5 mmol) Cs2CO3. The prepared catalyst had the composition of
PMθι2V03~2Csι~2Cu0 ι~o 5Fe0 oι~o ιOx (x is a number satisfying the valence requirements) and a surface Scanning Electron Microscopy (SEM) image of the catalyst is shown in FIG. 1. The SEM image shows that 11 scale bars are written in 200 nm, and thus, a distance between the bars is 20 nm. This is also applied to Figures illustrated in the following Examples and Comparative Examples.
[Example 3] A catalyst was prepared in the same manner as in Example 2 except that pyridine was not used. A surface SEM image of the catalyst is shown in FIG. 2.
[Comparative Example 1] A catalyst was prepared in the same manner as in Example 1 except that 3.6g (15.4 mmol) of Cu(NO3)2 and 15.0g (77 mmol) of CsNO3 were used instead of 1.7g (7.7 mmol) of Cu(OH)2 • CuCO3 and 12.55g (38.5 mmol) of Cs2CO3. A surface SEM image of the catalyst is shown in FIG. 3.
[Comparative Example 2] A catalyst was prepared in the same manner as in Comparative Example 1 except that the transition metal precursors and nitric acid underwent coprecipitation like U.S. Patent No. 6,458,740B2. A surface SEM image of the catalyst is shown in FIG. 4.
[Comparative Example 3] A commercially available catalyst was evaluated for catalyst performance and a
surface SEM image of the catalyst is shown in FIG. 5.
Catalytic reaction results for the catalysts of Examples 1-3 and Comparative Examples 1-3 are presented in Table 1 below. For catalyst activity evaluation, catalysts with a particle size of 150-250μm obtained by pulverization of calcined pellets were used to minimize the effect of the pressure change. Catalytic reaction was performed under the composition of 3.6 mol% of methacrolein (MACR), 10 mol% of H2O, 9.2 mol% of O2, and balance N2. A dose of a used catalyst was lg. The reaction temperature was 280-320 °C . A product was quantified by Gas Chromatography (GC). Methacrolein conversion rate, and methacrylic acid yield and selectivity were respectively calculated by Equations 1-3 below: [Equation 1 ] Methacrolein conversion rate (%) = [moles of reacted methacrolein / moles of supplied methacrolein] X 100 [Equation 2] Selectivity (%) = [moles of produced methacrylic acid / moles of reacted methacrolein] x 100 [Equation 3] Yield (%) = [moles of produced methacrylic acid / moles of supplied methacrolein] 100 = conversion rate x selectivity
Table 1
As can be seen from Table 1, the catalysts prepared in Examples 1-3 according to the present invention exhibited remarkably excellent conversion rate, selectivity, and yield, as compared with the catalysts of Comparative Examples 1-3 according to conventional technologies. In connection with the catalysts shown in FIGS. 1 and 2 according to the present invention, particles of 20 to 100 nm in size were uniformly distributed on surfaces of the catalysts, relative to the catalysts of Comparative Examples 1-3. This shows that transition metal ions were uniformly dispersed.
Industrial Applicability As apparent from the above description, a heteropolyacid catalyst of the present invention is excellent in conversion rate, selectivity, and yield, relative to that produced by a conventional heteropolyacid catalyst production technology.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims
What is claimed is: 1. A heteropolyacid catalyst represented by the following formula 1 : PMOaAbBeCdDeEfOg (1) wherein A is V, Nb, or W; B is an alkaline metal or an alkaline earth metal; C is Cu, Ag, Co, Ni, Pb, Mn, or Tl; D is Fe, Ce, Cr, Sn, Zn, Pd, or Rh; E is an organic acid or a N-containing compound; a is 5-12; b is 0.01-5; c is 0.01-3; d is 0.01-3; e is 0-0.3; f is 0-10; and g is a number satisfying the valence requirements of a, b, c, d, e, and f.
2. The heteropolyacid catalyst of claim 1, which has a composition of PMoι2V03-2Csι- Cuo l-o 5Feo oι~o ιOx where x is a number satisfying the valence requirements.
3. A method for producing the heteropolyacid catalyst of claim 1, the method comprising: (a) mixing (NH4)6Mo7O24, (NH4)VO4, and H3PO, and pyridine in some cases, to prepare an aqueous solution; (b) adding nitric acid to the solution of step (a) to prepare an ammonium ion- containing heteropolyacid; (c) adding a transition metal carbonate to a solution obtained in step (b); and (d) drying and calcining a catalyst-containing solution obtained in step (c) in an air atmosphere.
4. The method of claim 3, wherein in step (c), a transition metal nitrate is further added.
5. The method of claim 3, wherein in step (c), the transition metal carbonate is added at a temperature of 20-60 °C .
6. The method of claim 4, wherein in step (c), the transition metal carbonate and nitrate are added at a temperature of 20-60 °C .
7. The method of claim 3, wherein particles formed on a surface of the heteropolyacid catalyst have a particle size of 20-100 nm.
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| PCT/KR2005/000008 WO2005065822A1 (en) | 2004-01-09 | 2005-01-04 | Novel heteropolyacid catalyst and method for producing the same |
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| EP1847555A1 (en) | 2006-04-18 | 2007-10-24 | Borealis Technology Oy | Multi-branched Polypropylene |
| KR101009893B1 (en) | 2007-04-06 | 2011-01-20 | 주식회사 엘지화학 | Novel method for preparing high purity heteropoly acid |
| KR100954049B1 (en) | 2007-06-13 | 2010-04-20 | 주식회사 엘지화학 | Method for preparing heteropoly acid catalyst |
| CN107824213B (en) * | 2017-04-08 | 2019-06-18 | 李励 | A kind of method that carried heteropoly acid catalyst prepares chronic obstructive pulmonary disease pharmaceutical intermediate |
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| CN116196950B (en) * | 2023-02-16 | 2024-05-24 | 北华大学 | Synthesis method of bimetal doped heteropolyacid catalyst and application of bimetal doped heteropolyacid catalyst in lignin conversion |
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| JP3702710B2 (en) | 1999-06-15 | 2005-10-05 | 住友化学株式会社 | Catalyst for producing methacrylic acid and method for producing methacrylic acid |
| JP3763246B2 (en) * | 2000-04-06 | 2006-04-05 | 住友化学株式会社 | Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid |
| US6812188B2 (en) * | 2000-09-21 | 2004-11-02 | Nippon Kayaku Kabushiki Kaisha | Catalyst for methacrylic acid production, coated catalyst, and process for producing the same |
| JP4671320B2 (en) * | 2000-09-21 | 2011-04-13 | 日本化薬株式会社 | Production of coated catalyst for methacrylic acid production |
-
2004
- 2004-01-09 KR KR1020040001574A patent/KR100557640B1/en active IP Right Grant
- 2004-12-30 US US11/024,809 patent/US7094727B2/en active Active
- 2004-12-31 TW TW093141798A patent/TWI292339B/en active
-
2005
- 2005-01-04 JP JP2005518334A patent/JP2006513033A/en active Pending
- 2005-01-04 CN CNB2005800000265A patent/CN100360230C/en active Active
- 2005-01-04 EP EP05704433.1A patent/EP1701792B1/en not_active Not-in-force
- 2005-01-04 WO PCT/KR2005/000008 patent/WO2005065822A1/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4152338A (en) * | 1975-10-02 | 1979-05-01 | Denka Chemical Corporation | Process of preparing anhydrides from alkanes |
| EP0442517A1 (en) * | 1990-02-15 | 1991-08-21 | Mitsubishi Rayon Co., Ltd. | Preparation process of catalysts for producing methacrylic acid |
| US5330954A (en) * | 1991-09-03 | 1994-07-19 | Elf Atochem, S.A. | Catalytic system and its application to the oxydehydrogenation of saturated carboxylic acids and the oxidation of aldehydes to acids |
| US20010029233A1 (en) * | 2000-03-07 | 2001-10-11 | Nippon Shokubai Co., Ltd | Method for preparing heteropolyacid catalyst and method for producing methacrylic acid |
Non-Patent Citations (2)
| Title |
|---|
| DATABASE WPI Week 200060 Thomson Scientific, London, GB; AN 2000-621115 XP002595940 -& JP 2000 202294 A (MITSUBISHI RAYON CO LTD) 25 July 2000 (2000-07-25) * |
| See also references of WO2005065822A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200523021A (en) | 2005-07-16 |
| TWI292339B (en) | 2008-01-11 |
| WO2005065822A1 (en) | 2005-07-21 |
| EP1701792B1 (en) | 2014-12-24 |
| KR20050073224A (en) | 2005-07-13 |
| JP2006513033A (en) | 2006-04-20 |
| CN100360230C (en) | 2008-01-09 |
| CN1798607A (en) | 2006-07-05 |
| US7094727B2 (en) | 2006-08-22 |
| US20050153831A1 (en) | 2005-07-14 |
| EP1701792A4 (en) | 2010-09-22 |
| KR100557640B1 (en) | 2006-03-10 |
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